Flame-resistant polycarbonate ABS blends

Details Flame-resistant polycarbonate ABS blends Flame-resistant polycarbonate ABS blends

2002-02-27

2003-03-04

Boykin, Terressa M. (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Processes of preparing a desired or intentional composition...

C524S100000, C524S117000, C524S127000, C524S700000

Reexamination Certificate

active

06528561

ABSTRACT:

The present invention relates to polycarbonate-ABS moulding compositions provided with phosphonate amines, which moulding compositions exhibit excellent flame protection and very good processing properties, the graft polymer being prepared by means of mass, solution or mass-suspension polymerisation processes.
U.S. Pat. Nos. 4,073,767 and 5,844,028 describe cyclic phosphorus compounds including phosphorinane rings as suitable flameproofing agents for polyurethanes, polycarbonates, polyesters and polyamides. In U.S. Pat. No. 4,397,750, particular cyclic phosphonate esters are described as efficient flameproofing agents for polypropylene and other polyolefins. U.S. Pat. Nos. 5,276,066 and 5,844,028 describe particular (1,3,2-dioxaphosphorinanemethane)-amines which are suitable flameproofing agents for polyurethanes, polyesters, styrene polymers, PVC, PVAc or polycarbonate.
U.S. Pat. No. 3,505,431, French Patent 1 371 139, U.S. Pat. Nos. 3,711,577, 4,054,544 describe acyclic triphosphonate amines, some of which are halogenated.
EP-A 0 640 655 describes moulding compositions of aromatic polycarbonate, styrene-containing copolymers and graft polymers, which moulding compositions can be rendered flame-resistant with monomeric and/or oligomeric phosphorus compounds.
In EP-A 0 363 608, flame-resistant polymer mixtures of aromatic polycarbonate, styrene-containing copolymer or graft copolymer and oligomeric phosphates are described as flameproofing additives. For some applications, such as, for example, mouldings inside casing parts, the dimensional stability of those mixtures under heat is often inadequate.
In U.S. Pat. No. 5,061,745, polymer mixtures of aromatic polycarbonate, ABS graft polymer and/or styrene-containing copolymer and monophosphates are described as flameproofing additives. The level of resistance of those mixtures to stress cracking is often inadequate for the production of thin-walled casing parts.
The object of the present invention is to provide polycarbonate/ABS blends having excellent flame resistance and excellent processing properties, such as improved flow properties, improved modulus of elasticity and reduced formation of a coating on the tool during the processing operation. That spectrum of properties is required especially in the case of applications in the field of data technology, such as, for example, for casings for monitors, printers, copiers, etc.
It has now been found that PC/ABS moulding compositions containing phosphonate amine in combination with graft polymer based on a diene rubber and prepared by means of mass, solution or mass-suspension polymerisation processes exhibit the desired properties.
Accordingly, the invention provides blends containing
A) from 40 to 99 parts by weight, preferably from 60 to 98.5 parts by weight, of aromatic polycarbonate and/or polyester carbonate,
B) from 0.5 to 60 parts by weight, preferably from 1 to 40 parts by weight, particularly preferably from 2 to 25 parts by weight, of graft polymer, prepared by means of mass, solution or mass-suspension polymerisation processes, of
B.1) from 50 to 99 wt. %, preferably from 65 to 98 wt. %, of one or more vinyl monomers with
B.2) from 50 to 1 wt. %, preferably from 35 to 2 wt. %, of one or more graft bases having a glass transition temperature <10° C., preferably <0° C., particularly preferably <−10° C.,
C) from 0 to 45 parts by weight, preferably from 0 to 30 parts by weight, particularly preferably from 2 to 25 parts by weight, of at least one thermoplastic polymer selected from the group of the vinyl (co)polymers and polyalkylene terephthalates,
D) from 0.1 to 30 parts by weight, preferably from 1 to 25 parts by weight, particularly preferably from 2 to 20 parts by weight, of phosphonate amine of formula (I)
A
3−y
—N—B
y
  (I),
 in which
A represents a radical of formula (IIa)
R
1
and R
2
are each independently of the other unsubstituted or substituted C
1
-C
10
-alkyl or unsubstituted or substituted C
6
-C
10
-aryl,
R
3
and R
4
are each independently of the other unsubstituted or substituted C
1
-C
10
-alkyl or unsubstituted or substituted C
6
-C
10
-aryl, or
R
3
and R
4
together represent unsubstituted or substituted C
3
-C
10
-alkylene,
y represents the numerical values 0, 1 or 2, and
the substituents B are each independently hydrogen, optionally halogenated C
2
-C
8
-alkyl, unsubstituted or substituted C
6
-C
10
-aryl,
E) from 0 to 5 parts by weight, preferably from 0.1 to 3 parts by weight, particularly preferably from 0.1 to 1 part by weight, most particularly preferably from 0.1 to 0.5 part by weight, of fluorinated polyolefin.
Component A
Aromatic polycarbonates and/or aromatic polyester carbonates which are suitable according to the invention as component A are known in the literature or can be prepared by processes which are known in the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the preparation of aromatic polyester carbonates see, for example, DE-OS 3 077 934).
The preparation of aromatic polycarbonates is carried out, for example, by reacting diphenols with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase boundary process, optionally using chain terminators, for example monophenols, and optionally using branching agents having a functionality of three or more, for example triphenols or tetraphenols.
Diphenols for the preparation of aromatic polycarbonates and/or aromatic polyester carbonates are preferably those of formula (III)
wherein
A represents a single bond, C
1
-C
5
-alkylene, C
2
-C
5
-alkylidene, C
5
-C
6
-cycloalkylidene, —O—, —SO—, —CO—, —S—, —SO
2
—, C
6
-C
12
-arylene, to which there may be condensed other aromatic rings optionally containing hetero atoms,
or a radical of formula (IV) or (V)
 each of the substituents B represents C
1
-C
12
-alkyl, preferably methyl, halogen, preferably chlorine and/or bromine,
the substituents x are each independently of the other 0, 1 or 2,
p represents 1 or 0, and
R
7
and R
8
can be selected individually for each X
1
and are each independently of the other hydrogen or C
1
-C
6
-alkyl, preferably hydrogen, methyl or ethyl,
X
1
represents carbon, and
m represents an integer from 4 to 7, preferably 4 or 5, with the proviso that at at least one atom X
1
, R
7
and R
8
are simultaneously alkyl.
Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C
1
-C
5
-alkanes, bis-(hydroxyphenyl)-C
5
-C
6
-cycloalkanes, bis-(hydroxyphenyl)ethers, bis-(hydroxyphenyl)sulfoxides, bis-(hydroxyphenyl)ketones, bis-(hydroxyphenyl)-sulfones and &agr;,&agr;-bis-(hydroxyphenyl)-diisopropylbenzenes and their derivatives brominated and/or chlorinated at the ring.
Particularly preferred diphenols are 4,4′-dihydroxydiphenyl, bisphenol A, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl-sulfone and their di- and tetra-brominated or -chlorinated derivatives, such as, for example, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
Special preference is given to 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A).
The diphenols may be used individually or in the form of any desired mixtures.
The diphenols are known in the literature or obtainable by processes known in the literature.
Suitable chain terminators for the preparation of thermoplastic aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert.-butylphenol or 2,4,6-tribromophenol, as well as long-chained alkylphenols, such as 4-(1,3-tetramethylbutyl)-phenol according to DE-OS 2 842 005 or monoalkylphenols or dia

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